Peptization agent and solid catalyst manufacturing method

ABSTRACT

Methods of solid catalyst manufacture using a peptization agent, a peptization agent, and formed solid catalyst materials are provided. The peptization agent includes one or more oxidized disulfide oil (“ODSO”) compounds. These ODSO compounds peptization agents are used to replace conventional acids used as peptization agents.

FIELD OF THE DISCLOSURE

The present disclosure relates in general to a peptization agent for usein solid catalyst manufacture, and methods of solid catalyst manufactureusing a peptization agent.

BACKGROUND OF THE DISCLOSURE

Solid catalyst manufacturing processes, which can vary considerably fromone catalyst to another, include bulk catalysts and supports, andimpregnated catalysts starting from preformed supports.

Typical catalyst preparation or manufacturing steps are: precipitation,hydrothermal transformation, decantation, filtration, centrifugation,washing, drying, crushing and grinding, sieving, kneading/mulling, andforming operations. The formed particles can be subjected to thermaltreatment, calcination. In certain embodiments, catalytically activematerials are impregnated on the surface of, and/or within the pores of,the bulk catalyst particles and/or catalyst support particles.

Precipitation involves the mixing of solutions or suspension ofmaterials, resulting in the formation of a precipitate, which may becrystalline or amorphous. Kneading/mulling of wet solid materialsusually leads to the formation of dough that is subsequently formed anddried. Often kneaded/mulled product is subjected to thermal treatment toobtain more intimate contact between components and better homogeneityby thermal diffusion and solid-state reactions. In certain catalystparticles, catalytically active materials (such as one or more activemetal components, which varies widely depending on the application) aresubsequently added by impregnation or incipient wetting methods.

The support characteristics determine the mechanical properties of thecatalyst, such as attrition resistance, hardness, and crushing strength.High surface area and proper pore-size distribution are generallyrequired. The pore-size distribution and other physical properties of acatalyst support prepared by precipitation are also affected by theprecipitation and the aging conditions of the precipitate as well as bysubsequent drying and forming, and optionally calcining.

The final shape and size of catalyst particles are determined in theforming step. Catalysts and catalyst supports are formed into severalpossible shapes such as spheres, cylindrical extrudates, or shaped formssuch as a trilobes or a quadrilobes. Spherical catalyst support catalystcan be obtained by “oil dropping,” whereby precipitation occurs upon thepouring of a liquid into a second immiscible liquid. Other sphericalprocesses include marmurizing. Non spherical shapes are obtained bymixing raw materials to form an extrudable dough which is extrudedthrough a die with perforations. The “spaghetti” extrudate is dried,calcined, and broken into short pieces. The typical length to diameterratio of the catalyst base varies, for instance, between 2 and 4.

In the forming steps, typically inert materials are used as binders.Such binder materials are used to increase the post-compressionadhesion, and facilitate making the catalyst particles in a desiredform. In this forming step, acids such as hydrochloric acid, sulfuricacid, nitric acid or acetic acid are used as peptization agents todeagglomerate the particles.

Within a typical refinery, there are by-product streams that must betreated or otherwise disposed of. The mercaptan oxidation process,commonly referred to as the MEROX process, has long been employed forthe removal of the generally foul smelling mercaptans found in manyhydrocarbon streams and was introduced in the refining industry overfifty years ago. Because of regulatory requirements for the reduction ofthe sulfur content of fuels for environmental reasons, refineries havebeen, and continue to be faced with the disposal of large volumes ofsulfur-containing by-products. Disulfide oil (DSO) compounds areproduced as a by-product of the MEROX process in which the mercaptansare removed from any of a variety of petroleum streams includingliquefied petroleum gas, naphtha, and other hydrocarbon fractions. It iscommonly referred to as a ‘sweetening process’ because it removes thesour or foul smelling mercaptans present in crude petroleum. The term“DSO” is used for convenience in this description and in the claims, andwill be understood to include the mixture of disulfide oils produced asby-products of the mercaptan oxidation process. Examples of DSO includedimethyldisulfide, diethyldisulfide, and methylethyldisulfide.

The by-product DSO compounds produced by the MEROX unit can be processedand/or disposed of during the operation of various other refinery units.For example, DSO can be added to the fuel oil pool at the expense of aresulting higher sulfur content of the pool. DSO can be processed in ahydrotreating/hydrocracking unit at the expense of higher hydrogenconsumption. DSO also has an unpleasant foul or sour smell, which issomewhat less prevalent because of its relatively lower vapor pressureat ambient temperature; however, problems exist in the handling of thisoil.

Commonly owned U.S. Pat. No. 10,807,947 which is incorporated byreference herein in its entirety discloses a controlled catalyticoxidation of MEROX process by-products DSO. The resulting oxidizedmaterial is referred to as oxidized disulfide oil (ODSO). As disclosedin 10,807,947, the by-product DSO compounds from the mercaptan oxidationprocess can be oxidized, in the presence of a catalyst. The oxidationreaction products constitute an abundant source of ODSO compounds,sulfoxides, sulfonates, sulfinates and sulfones.

The ODSO stream co-produced contains ODSO compounds as disclosed in U.S.Pat. No. 10,781,168 as a solvent (in general), in U.S. Pat. No.10,793,782 as an aromatics extraction solvent, and in U.S. Pat. No.10,927,318 as a lubricity additive, all of which are incorporated byreference herein in their entireties. In the event that a refiner hasproduced or has on hand an amount of DSO compounds that is in excess offoreseeable needs for these or other uses, the refiner may wish todispose of the DSO compounds in order to clear a storage vessel and/oreliminate the product from inventory for tax reasons.

Thus, there is a clear and long-standing need to provide an efficientand economical process for the treatment of the large volumes of DSOby-products and their derivatives to effect and modify their propertiesin order to facilitate and simplify their environmentally acceptabledisposal, and to utilize the modified products in an economically andenvironmentally friendly manner, and thereby enhance the value of thisclass of by-products to the refiner.

In regard to the above background information, the present disclosure isdirected to provide a technical solution for an effective peptizationagent used in the manufacture of solid catalyst particles and/or solidcatalyst support particles.

SUMMARY OF THE DISCLOSURE

In certain embodiments a composition comprises a peptization agent usedto peptize a mixture of solid catalyst components in manufacture ofsolid catalyst particles and/or solid catalyst support particles, wherethe composition includes one or more ODSO compounds. In certainembodiments composition comprises a mixture of solid catalyst componentsand a peptization agent including one or more ODSO compounds. In certainembodiments composition comprises a first intermediate compositioncomprising one or more base catalyst materials and/or one or more basecatalyst support materials, a second intermediate composition comprisingone or more inorganic oxide materials, and a peptization agent includingone or more ODSO compounds.

In certain embodiments a method for manufacture of solid catalystparticles and/or solid catalyst support particles is provided,comprising contacting a mixture of solid catalyst components with aneffective quantity of the peptization agent including one or more ODSOcompounds to form a peptized composite, and forming solid catalystparticles and/or solid catalyst support particles from the composite.

In certain embodiments a method for manufacture of solid catalystparticles and/or solid catalyst support particles is disclosed,comprising: providing a first intermediate composition comprising one ormore base catalyst materials and/or one or more base catalyst supportmaterials. A second intermediate composition is provided comprising oneor more inorganic oxide materials. The first and second intermediatecompositions are mixed, and the admixture is contacted with an effectivequantity of a peptization agent including one or more ODSO compounds toform a peptized composite. Solid catalyst particles and/or solidcatalyst support particles are formed from the composite.

In certain embodiments, solid catalyst particles and/or solid catalystsupport particles formed according to the above method are provided,containing sulfur from the ODSO within the particles. In certainembodiments, the so-formed solid catalyst particles and/or solidcatalyst support particles exhibit similar crush strength compared toanalogous solid catalyst particles and/or solid catalyst supportparticles formed with conventional peptization agents.

Still other aspects, embodiments, and advantages of these exemplaryaspects and embodiments, are discussed in detail below. Moreover, it isto be understood that both the foregoing information and the followingdetailed description are merely illustrative examples of various aspectsand embodiments, and are intended to provide an overview or frameworkfor understanding the nature and character of the claimed aspects andembodiments, and serve to explain principles and operations of thedescribed and claimed aspects and embodiments. Any combinations of thevarious embodiments and implementations disclosed herein can be used.These and other aspects and features can be appreciated from thefollowing description of certain embodiments and the accompanyingdrawings and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The process of the disclosure will be described in more detail below andwith reference to the attached drawings.

FIG. 1 is a simplified schematic flow chart of a solid catalystmanufacturing process.

FIG. 2 is a simplified schematic diagram of a generalized version of aconventional mercaptan oxidation or MEROX process for the liquid-liquidextraction of a mercaptan containing hydrocarbon stream.

FIG. 3 is a simplified schematic diagram of a generalized version of anenhanced mercaptan oxidation or E-MEROX process.

FIG. 4A is the experimental ¹H-NMR spectrum of the polar, water-solublesolvent composition used in the example herein.

FIG. 4B is the experimental ¹³C-DEPT-135-NMR spectrum of the polar,water-soluble solvent composition used in the example herein.

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS OF THE DISCLOSURE

Methods of solid catalyst manufacture using a peptization agent, apeptization agent, and formed solid catalyst materials are provided. Thepeptization agent includes one or more ODSO compounds that replaceconventional acids used as peptization agents.

Embodiments of the present disclosure are directed to a peptizationagent used in the manufacture of solid catalyst particles and/or solidcatalyst support particles comprising, consisting of or consistingessentially of: (a) one or more ODSO compounds; (b) ODSO compoundspresent in an effluent refinery hydrocarbon stream recovered followingcatalytic oxidation of mercaptans present in a petroleum feedstream; (c)non-polar water-insoluble ODSO compounds present in an effluent refineryhydrocarbon stream recovered following catalytic oxidation of mercaptanspresent in a petroleum feedstream; and/or (d) polar water-soluble ODSOcompounds present in an effluent refinery hydrocarbon stream recoveredfollowing catalytic oxidation of mercaptans present in a petroleumfeedstream.

Embodiments of the present disclosure are directed to method ofmanufacturing solid catalyst particles and/or solid catalyst supportparticles including: providing one or more solid base catalyst materialsand/or solid base catalyst support materials; providing a solidinorganic oxide material; thoroughly mixing the solid materials to forman intimate mixture; and contacting the intimate mixture with the hereindescribed peptization agent to provide a peptized composite. The term“solid catalyst particles” refers to particles that have inherentcatalytic properties, such as acidic zeolites. The term “solid catalystsupport particles” refers to typically inert support materials. Incertain embodiments, active component materials can be incorporated inwith the solid mixture of base materials and the inorganic oxidematerial. The solid catalyst particles and/or solid catalyst supportparticles formed using the described peptization agent includequantities of sulfur within the final composition. The solid catalystparticles and/or solid catalyst support particles formed using thedescribed peptization agent exhibits similar crush strength as comparedto analogous solid catalyst particles and/or solid catalyst supportparticles formed with conventional peptization agents. By “analogoussolid catalyst particles and/or solid catalyst support particles formedwith conventional peptization agents” it is intended to describe theequivalent proportions of all materials with the exception of thepeptization agents. While not wishing to be bound by theory, the sulfurin ODSO remains in the extrudate due to reaction with inorganic oxidessuch as alumina, amorphous silica alumina and/or zeolites to enhancebinding compared to conventional peptization agents.

FIG. 1 shows a simplified schematic flow chart of a solid catalystmanufacturing process. One or more solid base catalyst materials and/orsolid base catalyst support materials 12 and one or more inorganic oxidematerials 14 are provided, which are mixed 16 to form a mixture 18. Oneor more base peptization agents 20 are provided, which is mixed andmulled 22 with the mixture 18 to produce a composite 24. The composite24 is formed 26 into solid catalyst particles 28 and/or solid catalystsupport particles 28. Not shown but readily apparent to those ofordinary skill in the art are additional steps that are used in certainknown catalyst manufacturing processes, including one or more additionalsteps of calcining the solid catalyst particles 28 and/or solid catalystsupport particles 28; impregnating the calcined particles with an activemetal component; and/or calcining the impregnated particles to form thefinal catalyst product.

As with known catalyst manufacturing processes, final shapes and sizesof catalyst particles are determined in the forming step 26. Catalystsand catalyst supports are formed into several possible shapes such asspheres, spheroids, cylindrical extrudates, or shaped forms such as atrilobes or a quadrilobes, using for instance suitable dies. Sphericalor spheroidal particles are be obtained by drop coagulation (also knownas “oil dropping”), whereby precipitation occurs upon the pouring of aliquid into a second immiscible liquid. Other spherical or spheroidalprocesses include marmurizing and spheronization after extrusion. Nonspherical shapes can be obtained by extrusion. For example, thecomposite 24 can be in the form of a wet extrudable dough or paste,which is extruded through a die with perforations, and the extrudate isdried, calcined, and broken into short pieces as the particles 28, forexample with a length to diameter particle ratio in the range of betweenabout 1.5-8, 1.5-5, 2-8, 2-5 and 2-4.

When preparing a composite 24, the one or more base catalyst materials12 and/or one or more base catalyst support materials 12, for examplewhich can be one or more of a zeolite, amorphous alumina silicate,silica, and/or metal salts, are bounded together with the one or moreinorganic oxide materials 14 before being extruded. In typical catalystand catalyst support manufacturing processes, binder materials formed ofinorganic oxide and peptization agents are added to increase thepost-compression adhesion, and facilitate making the catalyst particlesin a desired form. In the process herein, one or more peptization agents20 are added to the mixture 18 to deagglomerate the particles. In someembodiments, the peptization agents peptize the surface of inorganicoxide particles, such as alumina, which promotes a hydrogel film; henceinterparticle sintering is facilitated during calcination. In someembodiments, the peptization agents peptize the surface of more basecatalyst materials 12 and/or one or more base catalyst support materials12, such as zeolite, amorphous silica-alumina or silica, which promotesa hydrogel film; hence interparticle sintering is facilitated duringcalcination.

In one embodiment, the peptization agent 20 is mixed 22 with the mixture18 to form an extrusion dough or paste as the composite 24. Additionalwater such as deionized water can be added during the dough preparation.The dough is then formed 26 by extrusion, whereby catalyst particles 28in pellet form are recovered after suitable cutting, drying andoptionally subsequent catalyst preparation steps.

In conventional processes peptization agents are an acid such ashydrochloric acid, sulfuric acid, nitric acid or acetic acid. In theprocess of the present disclosure, a peptization agent used in themanufacture of solid catalyst particles and/or solid catalyst supportparticles comprising, consisting of or consisting essentially of: (a)one or more ODSO compounds; (b) ODSO compounds present in an effluentrefinery hydrocarbon stream recovered following catalytic oxidation ofmercaptans present in a petroleum feedstream; (c) non-polarwater-insoluble ODSO compounds present in an effluent refineryhydrocarbon stream recovered following catalytic oxidation of mercaptanspresent in a petroleum feedstream; and/or (d) polar water-soluble ODSOcompounds present in an effluent refinery hydrocarbon stream recoveredfollowing catalytic oxidation of mercaptans present in a petroleumfeedstream.

As is known in the field of manufacturing base catalyst materials and/orbase catalyst support materials, additional components can be added tothe paste or dough, including but not limited to plasticizing agentssuch as starches or cellulose ethers (for example commercially availableunder the trade name Methocel® from DuPont), or lubricating agents.Further, the binder material can be combined with porogenic materialsthat are dissolved or sintered after final formation of the catalystparticles to create pores.

Inorganic oxides that used in the related art of catalyst manufacturecan be used. Examples thereof include alumina, silica, titania,silica-alumina, alumina-titania, alumina-zirconia, alumina-boria,phosphorus-alumina, silica-alumina-boria, phosphorus-alumina-boria,phosphorus-alumina-silica, silica-alumina-titania, andsilica-alumina-zirconia. In certain embodiments, the inorganic oxidecontains alumina, and its can be provided in a form including, withoutlimitation, one or more of aluminum colloids, aluminates, boehmites,pseudo-boehmites, aluminum salts such as aluminum nitrate, aluminumsulfate and alumina chloride, aluminum hydroxides and alkoxides,aluminum wire and alumina gels. For example, suitable materials asalumina sources are commercially available from Sasol, for instance highpurity aluminas (CERALOX) and alumina hydrates (PURAL and CATAPAL),boehmites (DISPERSAL and DISPAL), and silica-alumina hydrates (SIRAL)and the corresponding oxides (SIRALOX).

In certain embodiments, the one or more base catalyst materials and/orone or more base catalyst support materials comprises, consists of orconsists essentially of zeolitic material, which are crystallinealumino-silicates. Hundreds of natural and synthetic zeolite frameworktypes exist, and have many different applications. Zeolites aregenerally hydrated aluminum silicates that can be made or selected witha controlled porosity and other characteristics. Certain types ofzeolites find application in various chemical reactions, for instancehydrocracking, hydrogenation, and isomerization processes in petroleumrefineries. The zeolite pores can form sites for catalytic reactions,and can also form channels that are selective for the passage of certaincompounds and/or isomers to the exclusion of others. Zeolites can alsopossess an acidity level that enhances its efficacy as a catalyticmaterial or adsorbent, alone or with the addition of active components.Suitable zeolitic materials include those identified by theInternational Zeolite Association, including .those with the identifiersABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFV,AFX, AFY, AHT, ANA, ANO, APC, APD, AST, ASV, ATN, ATO, ATS, ATT, ATV,AVE, AVL, AWO, AWW, BCT, BEC, BIK, BOF, BOG, BOZ, BPH, BRE, BSV, CAN,CAS, CDO, CFI, CGF, CGS, CHA, -CHI, -CLO, CON, CSV, CZP, DAC, DDR, DFO,DFT, DOH, DON, EAB, EDI, EEI, EMT, EON, EPI, ERI, ESV, ETL, ETR, ETV,EUO, EWO, EWS, EZT, FAR, FAU, FER, FRA, GIS, GIU, GME, GON, GOO, HEU,IFO, IFR, -IFT, -IFU, IFW, IFY, IHW, IMF, IRN, IRR, -IRY, ISV, ITE, ITG,ITH, ITR, ITT, -ITV, ITW, IWR, IWS, IWV, IWW, JBW, JNT, JOZ, JRY, JSN,JSR, JST, JSW, KFI, LAU, LEV, LIO, -LIT, LOS, LOV, LTA, LTF, LTJ, LTL,LTN, MAR, MAZ, MEI, MEL, MEP, MER, MFI, MFS, MON, MOR, MOZ, MRT, MSE,MSO, MTF, MTN, MTT, MTW, MVY, MWF, MWW, NAB, NAT, NES, NON, NPO, NPT,NSI, OBW, OFF, OKO, OSI, OSO, OWE, -PAR, PAU, PCR, PHI, PON, POR, POS,PSI, PTO, PTT, PTY, PUN, PWN, PWO, PWW, RHO, -RON, RRO, RSN, RTE, RTH,RUT, RWR, RWY, SAF, SAO, SAS, SAT, SAV, SBE, SBN, SBS, SBT, SEW, SFE,SFF, SFG, SFH, SFN, SFO, SFS, SFW, SGT, SIV, SOD, SOF, SOR, SOS, SOV,SSF, SSY, STF, STI, STT, STW, -SVR, SVV, SWY, -SYT, SZR, TER, THO, TOL,TON, TSC, TUN, UEI, UFI, UOS, UOV, UOZ, USI, UTL, UWY, VET, VFI, VNI,VSV, WEI, -WEN, YFI, YUG, ZON, *BEA, *CTH, *-EWT, *-ITN, *MRE, *PCS,*SFV, *-SSO, *STO, *-SVY, *UOE. For example, certain known zeolites usedin the petroleum refining industry include but are not limited tomordenite, ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, beta-type(*BEA), Y, USY, and MCM zeolites such as MCM-41 and MCM-48. For example,these can be (FAU) framework, which includes USY, having a microporesize related to the 12-member ring when viewed along the [111] directionof 7.4×7.4 Å; (MFI) framework, which includes ZSM-5, having a microporesize related to the 10-member rings when viewed along the [100] and[010] directions of 5.5×5.1 Å and 5.6×5.3 Å, respectively; (MEL)framework, which includes ZSM-11, having a micropore size related to the10-member ring when viewed along the [100] direction of 5.4×5.3 Å; (MTW)framework, which includes ZSM-12, having a micropore size related to the12-member ring when viewed along the [010] direction of 5.6×6.0 Å; (TON)framework, which includes ZSM-12, having a micropore size related to the10-member ring when viewed along the [001] direction of 4.6×5.7 Å; (MTT)framework, which includes ZSM-23, having a micropore size related to the10-member ring when viewed along the [001] direction of 4.5×5.2 Å; (FER)framework, which includes ZSM-35, having a micropore size related to the10-member ring and 8-member ring when viewed along the [001] and [010]directions of 4.2×5.4 Å and 3.5×4.8 Å, respectively; (MOR) framework,which includes mordenite zeolites, having a micropore size related tothe 12-member ring and 8-member ring when viewed along the [001] and[001] directions of 6.5×7.0 Å and 2.6×5.7 Å, respectively; and (*BEA)framework, which includes zeolite beta polymorph A, having a microporesize related to the 12-member rings when viewed along the [100] and[001] directions of 6.6×6.7 Å and 5.6×5.6 Å, respectively. Zeolite-typematerials are also known, such as crystalline silico-alumino-phosphate(SAPO) or alumino-phosphate (AlPO) materials.

In certain embodiments, the one or more base catalyst materials and/orone or more base catalyst support materials comprises, consists of orconsists essentially of amorphous silica-alumina (ASA). ASA can be usedas a catalytic material, or a support or co-support for a catalyticmaterial, in many commercial applications. Numerous methods ofmanufacturing ASA are known, and it is appreciated that the physical andcatalytic properties of ASA can be highly dependent upon the method bywhich it is manufactured. Conventional processes for making ASA areknown, for example as disclosed in U.S. Pat. Nos. 4,500,645, 8,795,513and 6,399,530, all of which are incorporated by reference herein intheir entireties.

In certain embodiments, the one or more base catalyst materials and/orone or more base catalyst support materials comprises, consists of orconsists essentially of silica. The silica source can comprise, withoutlimitation, one or more of silicates including sodium silicate (waterglass), rice husk, fumed silica, precipitated silica, colloidal silica,silica gels, other zeolites, dealuminated zeolites, and siliconhydroxides and alkoxides. Silica sources resulting in a high relativeyield are suitable. For instance, suitable materials as silica sourcesare commercially available from Cabot (for example, fumed silica) andLudox (for example, colloidal silica).

In certain embodiments, the one or more base catalyst materials and/orone or more base catalyst support materials comprises, consists of orconsists essentially of metal salts. Suitable metal salts include butare not limited to titanium oxide, zirconium oxide, alumina phosphate ormagnesium oxide.

Certain ratios of materials are provided to attain the effectivequantities of components as is known in catalyst manufacturing. The oneor more base catalyst materials and/or one or more base catalyst supportmaterials can comprise about 1-99, 1-90, 1-80, 1-50, 1-25, 5-99, 5-90,5-80, 5-50, 5-25, 10-99, 10-90, 10-80, 10-50 or 1-25 mass percent of thetotal finished catalyst particles, with the remainder being theinorganic oxide material and the peptization agent.

The solid catalyst particles and/or solid catalyst support particlesformed according to the process herein is a composite of (i) one or morebase catalyst materials and/or base catalyst support materials and (ii)a peptized binder material, wherein the peptization agent comprises,consists of or consists essentially of ODSO or a mixture of ODSOcompounds. In certain embodiments, the solid catalyst particles and/orsolid catalyst support particles formed herein have an average dimensionof about 0.1-5, 0.5-5, 1-5, 0.1-3, 0.5-3 or 1-3 millimeters (forinstance a diameter dimension, where the particles are extrudates with alength to diameter ratio in the range of between about 1.5-8, 1.5-5,2-8, 2-5 and 2-4). In certain embodiments, the solid catalyst particlesand/or solid catalyst support particles formed herein have an averageradial crush strength (as determined by ASTM D6175-03) is in the rangeof about 20-40 or 20-30 Newtons (N) per millimeter. “Radial crushstrength” is the force required to fracture or crush a material, such asthe formed (e.g., extruded) catalyst or catalyst support particles withcompression on the sides.

Example embodiments of the present disclosure are directed to one ormore ODSO compounds that are used as peptization agents. The peptizationagents can be a mixture that comprises two or more ODSO compounds. Inthe description herein, the terms “oxidized disulfide oil”, “ODSO”,“ODSO mixture” “ODSO composition” and “ODSO compound(s)” may be usedinterchangeably for convenience. As used herein, the abbreviations ofoxidized disulfide oils (“ODSO”) and disulfide oils (“DSO”) will beunderstood to refer to the singular and plural forms, which may alsoappear as “DSO compounds” and “ODSO compounds,” and each form may beused interchangeably. In certain instances, a singular ODSO compound mayalso be referenced.

In certain embodiments, an effective amount of ODSO as peptization agentherein can be quantified on as a mass ratio of ODSO to the bindermaterials (volatile free), in the range of about 1:1 to 1:1000, 1:1 to1:500, 1:1 to 1:100, 1:1 to 1:50, 1:1 to 1:20, 1:1 to 1:10, 1:2 to1:1000, 1:2 to 1:500, 1:2 to 1:100, 1:2 to 1:50, 1:2 to 1:20 or 1:2 to1:10. Volatile free mass is defined as the actual mass of the solidmaterials without considering the volatile fraction. In the examplesused herein, the volatile free mass is the mass after exposing thematerial to dry air at 600° C. for 1 hour.

In certain embodiments, an effective amount of ODSO as peptization agentherein can be quantified as a peptization level, quantity of peptizationagent (dry mass) to the quantity of total solid materials in theextrusion dough (volatile free mass) including the (1) inorganic oxidematerial and (2) zeolite or other base catalyst materials and/or basecatalyst support materials. An effective amount of ODSO as peptizationagent in the embodiments herein include quantities that result in asuitable peptization level, for instance between about 0.1-50, 0.1-40,0.1-25, 0.2-50, 0.2-40, 0.2-25, 0.5-50, 0.5-40, 0.5-25, 1-50, 1-40 or1-25%.

In certain embodiments, ODSO is used as a peptization agent in a pureundiluted state. In certain embodiments, ODSO mixed with water togenerate a peptization solution. For example, the mass ratio of ODSO towater in the peptization agent solution is in the range of about 100:0to 0.1:99.9, 100:0 to 1:99, 100:0 to 5:95, 100:0 to 10:90, 100:0 to20:80 or 100:0 to 50:50.

In certain embodiments, the peptization agent comprises, consists of orconsists essentially of ODSO in the presence of water. In certainembodiments, the peptization agent comprises, consists of or consistsessentially of ODSO, and wherein water is provided to thebinder/peptization agent in a separate step. In certain embodiments, thepeptization agent comprises ODSO in combination with one or more otherknown peptization agents, that is, conventional acids such ashydrofluoric acid, hydrochloric acid, sulfuric acid, nitric acid, aquaregia (a mixture of nitric acid and hydrochloric acid, optimally in amolar ratio of nitric:hydrochloric of 1:3) or acetic acid. Accordingly,the total peptization agent solution mass ratio of ODSO to conventionalacid (excluding water) is in the range of about 100:0 to 0.1:99.9, 100:0to 1:99, 100:0 to 5:95, 100:0 to 10:90, 100:0 to 20:80 or 100:0 to50:50.

In certain embodiments, the ODSO compounds used as the peptization agentor as a component thereof are obtained from controlled catalyticoxidation of disulfide oils from mercaptan oxidation processes. Theeffluents from controlled catalytic oxidation of disulfide oils frommercaptan oxidation processes includes ODSO compounds and in certainembodiments DSO compounds that were unconverted in the oxidationprocess. In certain embodiments this effluent contains water-solublecompounds and water-insoluble compounds. The effluent contains at leastone ODSO compound, or a mixture of two or more ODSO compounds, selectedfrom the group consisting of compounds having the general formula(R—SO—S—R′), (R—SOO—S—R′), (R—SOO—SO—R′), (R—SOO—SOO—R′), (R—SO—SO—R′),(R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SO—SO—OH), (R—SOO—SO—OH), (X—SO—OR)and (X—SOO—OR). In certain embodiments, in the above formula R and R′are alkyl or aryl groups comprising 1-10 carbon atoms. Further, Xdenotes esters and is (R—SO) or (R—SOO), with R as defined above. Itwill be understood that since the source of the DSO is a refineryfeedstream, the R and X substituents vary, e.g., methyl and ethylsubgroups, and the number of sulfur atoms, S, in the as-receivedfeedstream to oxidation can extend to 3, for example, trisulfidecompounds.

In certain embodiments the water-soluble compounds and water-insolublecompounds are separated from one another, and the ODSO acid or ODSO acidmixture comprise all or a portion of the water-soluble compoundsseparated from the total effluents from oxidation of disulfide oils frommercaptan oxidation processes. For example, the different phases can beseparated by decantation or partitioning with a separating funnel,separation drum, by decantation, or any other known apparatus or processfor separating two immiscible phases from one another. In certainembodiments, the water-soluble and water-insoluble components can beseparated by distillation as they have different boiling point ranges.It is understood that there will be crossover of the water-soluble andwater-insoluble components in each fraction due to solubility ofcomponents, typically in the ppmw range (for instance, about 1-10,000,1-1,000, 1-500 or 1-200 ppmw). In certain embodiments, contaminants fromeach phase can be removed, for example by stripping or adsorption.

In certain embodiments the peptization agent used herein in themanufacture of solid catalyst particles and/or solid catalyst supportparticles comprises, consists of or consists essentially of at least oneODSO compound that is selected from the group consisting of compoundshaving the general formula (R—SO—S—R′), (R—SOO—S—R′), (R—SOO—SO—R′),(R—SOO—SOO—R′), (R—SO—SO—R′), (R—SO—SOO—OH), (R—SOO—SOO—OH),(R—SO—SO—OH), (R—SOO—SO—OH), (X—SO—OR) and (X—SOO—OR). In certainembodiments the peptization agent herein comprises, consists of orconsists essentially of a mixture of two or more ODSO compounds that isselected from the group consisting of compounds having the generalformula (R—SO—S—R′), (R—SOO—S—R′), (R—SOO—SO—R′), (R—SOO—SOO—R′),(R—SO—SO—R′), (R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SO—SO—OH),(R—SOO—SO—OH), (X—SO—OR) and (X—SOO—OR). In certain embodiments thepeptization agent herein comprises, consists of or consists essentiallyof at least one water-soluble ODSO compound that is selected from thegroup consisting of compounds having the general formula (R—SOO—SO—R′),(R—SOO—SOO—R′), (R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SOO—SO—OH), (X—SO—OR)and (X—SOO—OR). In certain embodiments a peptization agent hereincomprises, consists of or consists essentially of a mixture of two ormore water-soluble ODSO compounds that is selected from the groupconsisting of compounds having the general formula (R—SOO—SO—R′),(R—SOO—SOO—R′), (R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SOO—SO—OH), (X—SO—OR)and (X—SOO—OR). In certain embodiments the ODSO compounds are selectedfrom the group consisting of (R—SOO—SO—R′), (R—SOO—SOO—R′),(R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SO—SO—OH), (R—SOO—SO—OH), and mixturesthereof. In certain embodiments, in the above formulae R and R′ arealkyl or aryl groups comprising 1-10 carbon atoms. Further, X denotesesters and is (R—SO) or (R—SOO), with R as defined above. In certainembodiments, the ODSO compound(s) used as a peptization agent have 1 to20 carbon atoms.

In certain embodiments, a peptization agent disclosed and used hereincomprises, consists of or consists essentially of ODSO compounds havingan average density greater than about 1.0 g/cc. In certain embodiments,a peptization agent disclosed and used herein comprises, consists of orconsists essentially of ODSO compounds having an average boiling pointgreater than about 80° C. In certain embodiments, a peptization agentdisclosed and used herein comprises, consists of or consists essentiallyof ODSO compounds having a dielectric constant that is less than orequal to 100 at 0° C.

Table 1 includes examples of ODSO compounds. ODSO compounds that contain1 and 2 oxygen atoms are non-polar and water-insoluble. ODSO compoundsthat contain 3 or more oxygen atoms are water-soluble. The production ofeither polar or non-polar ODSO compounds is in part dependent on thereaction conditions during the oxidation process. The ODSO compoundsthat contain 3 or more oxygen atoms are water-soluble over effectivelyall concentrations, for instance, with some minor amount of acceptabletolerance for carry over components from the effluent stream and in thewater-insoluble fraction with 2 oxygen atoms of no more than about 1, 3or 5 mass percent.

In certain embodiments of the disclosed peptization agents, all or aportion of mixtures formed by the controlled catalytic oxidation ofMEROX process by-products DSO disclosed in 10,807,947 discussed above,are highly effective as peptization agents in the manufacture and usedherein correspond to oxidized DSO compounds present in an effluentrefinery hydrocarbon stream recovered following the catalytic oxidationof mercaptans present in the hydrocarbon stream. In some embodiments,the DSO compounds are oxidized in the presence of a catalyst.

As noted above, the designation “MEROX” originates from the function ofthe process itself, that is, the conversion of mercaptans by oxidation.The MEROX process in all of its applications is based on the ability ofan organometallic catalyst in a basic environment, such as a caustic, toaccelerate the oxidation of mercaptans to disulfides at near ambienttemperatures and pressures. The overall reaction can be expressed asfollows:

RSH+¼O₂→½RSSR+½H₂O  (1)

where R is a hydrocarbon chain that may be straight, branched, orcyclic, and the chains can be saturated or unsaturated. In mostpetroleum fractions, there will be a mixture of mercaptans so that the Rcan have 1, 2, 3 and up to 10 or more carbon atoms in the chain. Thisvariable chain length is indicated by R and R′ in the reaction. Thereaction is then written:

2R′SH+2RSH+O₂→2R′SSR+2H₂O  (2)

This reaction occurs spontaneously whenever any sour mercaptan-bearingdistillate is exposed to atmospheric oxygen, but proceeds at a very slowrate. In addition, the catalyzed reaction (1) set forth above requiresthe presence of an alkali caustic solution, such as aqueous sodiumhydroxide. The mercaptan oxidation proceeds at an economically practicalrate at moderate refinery downstream temperatures.

The MEROX process can be conducted on both liquid streams and oncombined gaseous and liquid streams. In the case of liquid streams, themercaptans are converted directly to disulfides which remain in theproduct so that there is no reduction in total sulfur content of theeffluent stream. The MEROX process typically utilizes a fixed bedreactor system for liquid streams and is normally employed with chargestocks having end points above 135° C.-150° C. Mercaptans are convertedto disulfides in the fixed bed reactor system over a catalyst, forexample, an activated charcoal impregnated with the MEROX reagent, andwetted with caustic solution. Air is injected into the hydrocarbonfeedstream ahead of the reactor and in passing through thecatalyst-impregnated bed, the mercaptans in the feed are oxidized todisulfides. The disulfides are substantially insoluble in the causticand remain in the hydrocarbon phase. Post treatment is required toremove undesirable by-products resulting from known side reactions suchas the neutralization of H₂S, the oxidation of phenolic compounds,entrained caustic, and others.

The vapor pressures of disulfides are relatively low compared to thoseof mercaptans, so that their presence is much less objectionable fromthe standpoint of odor; however, they are not environmentally acceptabledue to their sulfur content and their disposal can be problematical.

In the case of mixed gas and liquid streams, extraction is applied toboth phases of the hydrocarbon streams. The degree of completeness ofthe mercaptan extraction depends upon the solubility of the mercaptansin the alkaline solution, which is a function of the molecular weight ofthe individual mercaptans, the extent of the branching of the mercaptanmolecules, the concentration of the caustic soda and the temperature ofthe system. Thereafter, the resulting DSO compounds are separated andthe caustic solution is regenerated by oxidation with air in thepresence of the catalyst and reused.

Referring to the attached drawings, FIG. 2 is a simplified schematic ofa generalized version of a conventional MEROX process employingliquid-liquid extraction for removing sulfur compounds. A MEROX unit1010, is provided for treating a mercaptan containing hydrocarbon stream1001. In some embodiments, the mercaptan containing hydrocarbon stream1001 is LPG, propane, butane, light naphtha, kerosene, jet fuel, or amixture thereof. The process generally includes the steps of:introducing the hydrocarbon stream 1001 with a homogeneous catalyst intoan extraction vessel 1005 containing a caustic solution 1002, in someembodiments, the catalyst is a homogeneous cobalt-based catalyst;passing the hydrocarbon catalyst stream in counter-current flow throughthe extraction section of the extraction 1005 vessel in which theextraction section includes one or more liquid-liquid contactingextraction decks or trays (not shown) for the catalyzed reaction withthe circulating caustic solution to convert the mercaptans towater-soluble alkali metal alkane thiolate compounds; withdrawing ahydrocarbon product stream 1003 that is free or substantially free ofmercaptans from the extraction vessel 1005, for instance, having no morethan about 1000, 100, 10 or 1 ppmw mercaptans; recovering a combinedspent caustic and alkali metal alkane thiolate stream 1004 from theextraction vessel 1005; subjecting the spent caustic and alkali metalalkane thiolate stream 1004 to catalyzed wet air oxidation in a reactor1020 into which is introduced catalyst 1005 and air 1006 to provide theregenerated spent caustic 1008 and convert the alkali metal alkanethiolate compounds to disulfide oils; and recovering a by-product stream1007 of DSO compounds and a minor proportion of other sulfides such asmono-sulfides and tri-sulfides. The effluents of the wet air oxidationstep in the MEROX process can comprise a minor proportion of sulfidesand a major proportion of disulfide oils. As is known to those skilledin the art, the composition of this effluent stream depends on theeffectiveness of the MEROX process, and sulfides are assumed to becarried-over material. A variety of catalysts have been developed forthe commercial practice of the process. The efficiency of the MEROXprocess is also a function of the amount of H₂S present in the stream.It is a common refinery practice to install a prewashing step for H₂Sremoval.

An enhanced MEROX process (“E-MEROX”) is a modified MEROX process wherean additional step is added, in which DSO compounds are oxidized with anoxidant in the presence of a catalyst to produce a mixture of ODSOcompounds. The by-product DSO compounds from the mercaptan oxidationprocess are oxidized, in some embodiments in the presence of a catalyst,and constitute an abundant source of ODSO compounds that are sulfoxides,sulfonates, sulfinates, sulfones and their corresponding di-sulfurmixtures. The disulfide oils having the general formula RSSR′ (wherein Rand R′ can be the same or different and can have 1, 2, 3 and up to 10 ormore carbon atoms) can be oxidized without a catalyst or in the presenceof one or more catalysts to produce a mixture of ODSO compounds. Theoxidant can be a liquid peroxide selected from the group consisting ofalkyl hydroperoxides, aryl hydroperoxides, dialkyl peroxides, diarylperoxides, peresters and hydrogen peroxide. The oxidant can also be agas, including air, oxygen, ozone and oxides of nitrogen. If a catalystis used in the oxidation of the disulfide oils having the generalformula RSSR′ to produce the ODSO compounds, it can be a heterogeneousor homogeneous oxidation catalyst. The oxidation catalyst can beselected from one or more heterogeneous or homogeneous catalystcomprising metals from the IUPAC Group 4-12 of the Periodic Table,including Ti, V, Mn, Co, Fe, Cr, Cu, Zn, W and Mo. The catalyst can be ahomogeneous water-soluble compound that is a transition metal containingan active species selected from the group consisting of Mo (VI), W (VI),V (V), Ti (IV), and their combination. In certain embodiments, suitablehomogeneous catalysts include molybdenum naphthenate, sodium tungstate,molybdenum hexacarbonyl, tungsten hexacarbonyl, sodium tungstate andvanadium pentoxide. An exemplary catalyst for the controlled catalyticoxidation of MEROX process by-products DSO is sodium tungstate,Na₂WO₄·2H₂O. In certain embodiments, suitable heterogeneous catalystsinclude Ti, V, Mn, Co, Fe, Cr, W, Mo, and combinations thereof depositedon a support such as alumina, silica-alumina, silica, natural zeolites,synthetic zeolites, and combinations comprising one or more of the abovesupports.

The oxidation of DSO typically is carried out in an oxidation vesselselected from one or more of a fixed-bed reactor, an ebullated bedreactor, a slurry bed reactor, a moving bed reactor, a continuousstirred tank reactor, and a tubular reactor. The ODSO compounds producedin the E-MEROX process generally comprise two phases: a water-solublephase and water-insoluble phase, and can be separated into the aqueousphase containing water-soluble ODSO compounds and a non-aqueous phasecontaining water-insoluble ODSO compounds. The E-MEROX process can betuned depending on the desired ratio of water-soluble to water-insolublecompounds presented in the product ODSO mixture. Partial oxidation ofDSO compounds results in a higher relative amount of water-insolubleODSO compounds present in the ODSO product and a near or almost completeoxidation of DSO compounds results in a higher relative amount ofwater-soluble ODSO present in the ODSO product. Details of the ODSOcompositions are discussed in the U.S. Pat. No. 10,781,168, which isincorporated herein by reference above.

FIG. 3 is a simplified schematic of an E-MEROX process that includesE-MEROX unit 1030. The MEROX unit 1010 unit operates similarly as inFIG. 2 , with similar references numbers representing similarunits/feeds. In FIG. 2 , the effluent stream 1007 from the generalizedMEROX unit of FIG. 2 is treated. It will be understood that theprocessing of the mercaptan containing hydrocarbon stream of FIG. 2 isillustrative only and that separate streams of the products, andcombined or separate streams of other mixed and longer chain productscan be the subject of the process for the recovery and oxidation of DSOto produce ODSO compounds, that is the E-MEROX process. In order topractice the E-MEROX process, apparatus are added to recover theby-product DSO compounds from the MEROX process. In addition, a suitablereactor 1035 is added into which the DSO compounds are introduced in thepresence of a catalyst 1032 and an oxidant 1034 and subjecting the DSOcompounds to a catalytic oxidation step to produce the mixed stream 1036of water and ODSO compounds. A separation vessel 1040 is provided toseparate the by-product 1044 from the ODSO compounds 1042.

The oxidation to produce OSDO can be carried out in a suitable oxidationreaction vessel operating at a pressure in the range from about 1-30,1-10 or 1-3 bars. The oxidation to produce OSDO can be carried out at atemperature in the range from about 20-300, 20-150, 20-90, 45-300,15-150 or 45-90° C. The molar feed ratio of oxidizingagent-to-mono-sulfur can be in the range of from about 1:1 to 100:1, 1:1to 30:1 or 1:1 to 4:1. The residence time in the reaction vessel can bein the range of from about 5-180, 5-90, 5-30, 15-180, 15-90 or 5-30minutes. In certain embodiments, oxidation of DSO is carried out in anenvironment without added water as a reagent. The by-products stream1044 generally comprises wastewater when hydrogen peroxide is used asthe oxidant. Alternatively, when other organic peroxides are used as theoxidant, the by-products stream 1044 generally comprises the alcohol ofthe peroxide used. For example, if butyl peroxide is used as theoxidant, the by-product alcohol 1044 is butanol.

In certain embodiments water-soluble ODSO compounds are passed to afractionation zone (not shown) for recovery following their separationfrom the wastewater fraction. The fractionation zone can include adistillation unit. In certain embodiments, the distillation unit can bea flash distillation unit with no theoretical plates in order to obtaindistillation cuts with larger overlaps with each other or,alternatively, on other embodiments, the distillation unit can be aflash distillation unit with at least 15 theoretical plates in order tohave effective separation between cuts. In certain embodiments, thedistillation unit can operate at atmospheric pressure and at atemperature in the range of from 100° C. to 225° C. In otherembodiments, the fractionation can be carried out continuously undervacuum conditions. In those embodiments, fractionation occurs at reducedpressures and at their respective boiling temperatures. For example, at350 mbar and 10 mbar, the temperature ranges are from 80° C. to 194° C.and 11° C. to 98° C., respectively. Following fractionation, thewastewater is sent to the wastewater pool (not shown) for conventionaltreatment prior to its disposal. The wastewater by-product fraction cancontain a small amount of water-insoluble ODSO compounds, for example,in the range of from 1 ppmw to 10,000 ppmw. The wastewater by-productfraction can contain a small amount of water-soluble ODSO compounds, forexample, in the range of from 1 ppmw to 50,000 ppmw, or 100 ppmw to50,000 ppmw. In embodiments where alcohol is the by-product alcohol, thealcohol can be recovered and sold as a commodity product or added tofuels like gasoline. The alcohol by-product fraction can contain a smallamount of water-insoluble ODSO compounds, for example, in the range offrom 1 ppmw to 10,000 ppmw. The alcohol by-product fraction can containa small amount of water-soluble ODSO compounds, for example, in therange of from 100 ppmw to 50,000 ppmw.

The ODSO that is obtained from a low value by-product disulfide oilstreams that were previously known as nuisances within a refinery cansubstitute for acids used as a peptization agent to treat a mixture ofsolid catalyst components in manufacture of solid catalyst particlesand/or solid catalyst support particles. Thus, the refinery wastebecomes a useful ingredient in catalyst manufacturing and a valuableindustrial commodity, as it eliminates nitric acid or other acidstypically used in the process, thereby reducing raw material cost of thecatalyst. The solid catalyst particles and/or solid catalyst supportparticles using ODSO as a peptization agent has similar strength andpressure resistant properties as compared to extrudates prepared withtraditional nitric acid as a peptization agent.

EXAMPLES

Comparative Example: A quantity of extrudates (pellets) withvolatile-free composition of 48 mass percent alumina (CATAPAL® C1 fromSasol Germany GmbH), 42 mass percent amorphous silica alumina (ASA)(Siral-40, Sasol Chemicals (USA) LLC) and 10 mass percent Y-zeolite(CBV720 from Zeolyst International, USA) was prepared. The solidmaterials were thoroughly mixed. As peptization agent, a nitric acidsolution with concentration of 4 mass percent was used to peptize thepowder mixture with peptization level of 4%. The mass ratio of nitricacid solution to the solids (volatile free) to be peptized is 0.31. Thenitric acid solution was added slowly to the solid mixture. Extensivemulling and mixing were performed while the nitric acid solution wasadded. The final mixture was targeted to have weight loss of 55% whencalcined at 600° C. for 1 hour. Pellets were prepared by extruding themixture using a Bonnot extruder equipped with 1/16 inch hole die-plate.The pellets were then calcined in air using a muff oven. Calcination wascarried out by: ramping the temperature from room temperature to 100° C.at 5° C./min; holding for 1 hour, ramping to 400° C. at 5° C./min;holding for 1 hour; ramping to 630° C. at 5° C./min; and holding for 1hour.

Reference Example ODSO compounds used in Examples 1-3 below wereproduced as disclosed in U.S. Pat. No. 10,781,168, incorporated byreference above, and in particular the fraction referred to therein asComposition 2. Catalytic oxidation a hydrocarbon refinery feedstockhaving 98 mass percent of C1 and C2 disulfide oils was carried out. Theoxidation of the DSO compounds was performed in batch mode under refluxat atmospheric pressure, that is, approximately 1.01 bar. The hydrogenperoxide oxidant was added at room temperature, that is, approximately23° C. and produced an exothermic reaction. The molar ratio ofoxidant-to-DSO compounds (calculated based upon mono-sulfur content) was2.40. After the addition of the oxidant was complete, the reactionvessel temperature was set to reflux at 80° C. for approximately onehour. Two immiscible layers formed, one a dark red to brown layer,hereinafter referred to as Composition 1, and a light-yellow layer,hereinafter referred to as Composition 2. A separating funnel was usedto separate and isolate each of the two layers. The catalyst used in theoxidation of the DSO compounds was sodium tungstate. The Composition 2,referred to herein as the selected water-soluble ODSO fraction, wasused. FIG. 4A is the experimental 1H-NMR spectrum of the polar,water-soluble ODSO mixture that is the selected water-soluble ODSOfraction in the example herein. FIG. 4B is the experimental¹³C-DEPT-135-NMR spectrum of the polar, water-soluble ODSO mixture thatis the selected water-soluble ODSO fraction in the example herein. Theselected water-soluble ODSO fraction was mixed with a CD₃OD solvent andthe spectrum was taken at 25° C. Methyl carbons have a positiveintensity while methylene carbons exhibit a negative intensity. Thepeaks in the 48-50 ppm region belong to carbon signals of the CD₃ODsolvent.

When comparing the experimental ¹³C-DEPT-135-NMR spectrum of FIG. 4B forthe selected water-soluble ODSO fraction with a saved database ofpredicted spectra, it was found that a combination of the predictedalkyl-sulfoxidesulfonate (R—SO—SOO—OH), alkyl-sulfonesulfonate(R—SOO—SOO—OH), alkyl-sulfoxidesulfinate (R—SO—SO—OH) andalkyl-sulfonesulfinate (R—SOO—SO—OH) most closely corresponded to theexperimental spectrum. This suggests that alkyl-sulfoxidesulfonate(R—SO—SOO—OH), alkyl-sulfonesulfonate (R—SOO—SOO—OH),alkyl-sulfoxidesulfinate (R—SO—SO—OH) and alkyl-sulfonesulfinate(R—SOO—SO—OH) are major compounds in the selected water-soluble ODSOfraction. It is clear from the NMR spectra shown in FIGS. 4A and 4B thatthe selected water-soluble ODSO fraction comprises a mixture of ODSOcompounds that form a peptization solution of the present disclosure.

Example 1: The process of the Comparative Example was followed, exceptthat a different peptization solution was used. The peptization solutionwas prepared by substituting nitric acid (dry) with equal mole of theselected water-soluble ODSO fraction relative to nitric acid. Whencalculating the mass of ODSO from moles in the Examples 1-3, an averagemolecular weight of 160 g/mol is assumed, which is the molecular weightof 1-Hydroxy-2-methyldisulfane 1,1,2,2-tetraoxide. The quantity of waterin the solution and the ratios of all other materials were the same asin the Comparative Example.

Example 2: The process of the Comparative Example was followed, exceptthat the peptization solution was prepared by substituting nitric acid(dry) with equal mass of the selected water-soluble ODSO fractionrelative to nitric acid, on a mass equivalent basis. The quantity ofwater in the solution and the ratios of all other materials were thesame as in the Comparative Example.

Example 3: The process of the Comparative Example was followed, exceptthat the peptization solution was prepared by substituting nitric acid(dry) with a proton[H+] release equivalent amount of the selectedwater-soluble ODSO fraction. Based a pH analysis, it is that 1.35 mol ofODSO can generate 1 mole of [H+] for the assumed molecular weight of 160in the Examples herein. The quantity of water in the solution wasreduced to maintain the same mass as the final solution in theComparative Example and the ratios of all other materials were the sameas in the Comparative Example.

Example Results and Analysis: Table 2 provides the crush strength andsulfur level for each example. The crush strength was measured by ASTMD6175-03. The sulfur level (shown as ratio of atomic sulfur in ODSOrelative to silica, normalized, and as ODSO quantity, normalized)sample. The examples clearly demonstrate that the extrudates made withODSO as a peptization agent for the binder have similar crush strength.The sulfur level has a strong correlation with the amount of ODSO usingduring preparation.

It is to be understood that not all components and/or steps describedand illustrated with reference to the figures are required for allembodiments or arrangements. Further, the terminology used herein is forthe purpose of describing particular embodiments only and is notintended to be limiting of the invention. As used herein, the singularforms “a”, “an” and “the” are intended to include the plural forms aswell, unless the context clearly indicates otherwise. It will be furtherunderstood that the terms ““including,” “comprising,” or “having,”“containing,” “involving,” and variations thereof herein, when used inthis specification, specify the presence of stated features, integers,steps, operations, elements, and/or components, but do not preclude thepresence or addition of one or more other features, integers, steps,operations, elements, components, and/or groups thereof.

It should be noted that use of ordinal terms such as “first,” “second,”“third,” etc., in the claims to modify a claim element does not byitself connote any priority, precedence, or order of one claim elementover another or the temporal order in which acts of a method areperformed, but are used merely as labels to distinguish one claimelement having a certain name from another element having a same name(but for use of the ordinal term) to distinguish the claim elements.

Notably, the figures and examples above are not meant to limit the scopeof the present disclosure to a single implementation, as otherimplementations are possible by way of interchange of some or all thedescribed or illustrated elements. Moreover, where certain elements ofthe present disclosure can be partially or fully implemented using knowncomponents, only those portions of such known components that arenecessary for an understanding of the present disclosure are described,and detailed descriptions of other portions of such known components areomitted so as not to obscure the disclosure. In the presentspecification, an implementation showing a singular component should notnecessarily be limited to other implementations including a plurality ofthe same component, and vice-versa, unless explicitly stated otherwiseherein. Moreover, applicants do not intend for any term in thespecification or claims to be ascribed an uncommon or special meaningunless explicitly set forth as such. Further, the present disclosureencompasses present and future known equivalents to the known componentsreferred to herein by way of illustration.

The foregoing description of the specific implementations will so fullyreveal the general nature of the disclosure that others can, by applyingknowledge within the skill of the relevant art(s), readily modify and/oradapt for various applications such specific implementations, withoutundue experimentation, without departing from the general concept of thepresent disclosure. Such adaptations and modifications are thereforeintended to be within the meaning and range of equivalents of thedisclosed implementations, based on the teaching and guidance presentedherein. It is to be understood that the phraseology or terminologyherein is for the purpose of description and not of limitation, suchthat the terminology or phraseology of the present specification is tobe interpreted by the skilled artisan in light of the teachings andguidance presented herein, in combination with the knowledge of oneskilled in the relevant art(s). It is to be understood that dimensionsdiscussed or shown are drawings accordingly to one example and otherdimensions can be used without departing from the disclosure.

The subject matter described above is provided by way of illustrationonly and should not be construed as limiting. Various modifications andchanges can be made to the subject matter described herein withoutfollowing the example embodiments and applications illustrated anddescribed, and without departing from the true spirit and scope of theinvention encompassed by the present disclosure, which is defined by theset of recitations in the following claims and by structures andfunctions or steps which are equivalent to these recitations.

TABLE 1 ODSO Name Formula Structure Examples Dialkyl-thiosulfoxide oralkyl-alkane-sulfinothioate (R-SO-S-R′)

S-Methyl methanesulfinothioate Dialkyl-thiosulfones or Alkyl-Alkane-thiosulfonate (R-SOO-S-R′)

Methyl Methanethiosulfonate Dialkyl-sulfonesulfoxide Or1,2-alkyl-alkyl-disulfane 1,1,2-trioxide (R-SOO-SO-R′)

1,2-Dimethyldisulfane 1,1,2- trioxide Dialkyl-disulfone Or 1,2alkyl-alkyl-disulfane 1,1,2,2-tetraxoide (R-SOO-SOO-R′)

1,2-Dimethyldisulfane 1,1,2,2-tetraoxide Dialkyl-disulfoxide(R-SO-SO-R′)

1,2-Dimethyldisulfane 1,2- dioxide Alkyl-sulfoxidesulfonate (R-SO-SOO-OH)

Methylsulfanesulfonic acid oxide Alkyl-sulfonesulfonate (R-SOO-SOO- OH)

1-Hydroxy-2-methyldisulfane 1,1,2,2-tetraoxide Alkyl-sulfoxidesulfinate(R-SO-SO-OH)

1-Hydroxy-2-methyldisulfane 1,2-dioxide Alkyl-sulfonesulfinate(R-SOO-SO-OH)

Methylsulfanesulfinic acid dioxide R and R′ can be the same or differentalkyl or aryl groups comprising 1-10 carbon atoms.

TABLE 2 Peptizing Agent Average Quantity Peptization Radial Crush(Normalized Example Agent Strength (N) to nitric acid) ComparativeNitric Acid 28.9 1.00 1 ODSO 21.9 2.39 2 ODSO 28.4 1.00 3 ODSO 20.9 3.60

1. (canceled)
 2. (canceled)
 3. (canceled)
 4. The method as in claim 9,wherein the one or more ODSO compounds is selected from the groupconsisting of compounds having the general formula (R—SO—S—R′),(R—SOO—S—R′), (R—SOO—SO—R′), (R—SOO—SOO—R′), (R—SO—SO—R′),(R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SO—SO—OH), (R—SOO—SO—OH), (X—SO—OR)and (X—SOO—OR), where R and R′ are alkyl or aryl groups comprising 1-10carbon atoms, and where X denotes esters and is (R—SO) or (R—SOO). 5.The method as in claim 9, wherein the one or more ODSO compounds isselected from the group consisting of water-soluble ODSO compoundshaving the general formula (R—SOO—SO—R′), (R—SOO—SOO—R′), (R—SO—SOO—OH),(R—SOO—SOO—OH), (R—SOO—SO—OH), (X—SO—OR) and (X—SOO—OR), where R and R′are alkyl or aryl groups comprising 1-10 carbon atoms, and where Xdenotes esters and is (R—SO) or (R—SOO).
 6. The method as in claim 9,wherein the peptization agent comprises a mixture of two or more typesof ODSO compounds selected from the group consisting of compounds havingthe general formula (R—SO—S—R′), (R—SOO—S—R′), (R—SOO—SO—R′),(R—SOO—SOO—R′), (R—SO—SO—R′), (R—SO—SOO—OH), (R—SOO—SOO—OH),(R—SO—SO—OH), (R—SOO—SO—OH), (X—SO—OR) and (X—SOO—OR), where R and R′are alkyl or aryl groups comprising 1-10 carbon atoms, and where Xdenotes esters and is (R—SO) or (R—SOO).
 7. The method as in claim 9,wherein the peptization agent comprises a mixture of two or more typesof water-soluble ODSO compounds selected from the group consisting ofcompounds having the general formula (R—SOO—SO—R′), (R—SOO—SOO—R′),(R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SOO—SO—OH), (X—SO—OR) and (X—SOO—OR),where R and R′ are alkyl or aryl groups comprising 1-10 carbon atoms,and where X denotes esters and is (R—SO) or (R—SOO).
 8. The method as inclaim 6, wherein the mixture of two or more types of ODSO compoundscorresponds to oxidized disulfide oils present in an effluent refineryhydrocarbon stream recovered following catalytic oxidation of mercaptanspresent in the effluent refinery hydrocarbon stream.
 9. A method formanufacture of solid catalyst particles and/or solid catalyst supportparticles comprising contacting a mixture of solid catalyst componentswith an effective quantity of a peptization agent to peptize the mixtureof solid catalyst components and form a peptized composite, and formingsolid catalyst particles and/or solid catalyst support particles fromthe peptized composite, wherein the peptization agent including one ormore oxidized disulfide oil (ODSO) compounds.
 10. A method formanufacture of solid catalyst particles and/or solid catalyst supportparticles comprising: providing a first intermediate compositioncomprising one or more base catalyst materials and/or one or more basecatalyst support materials; providing a second intermediate compositioncomprising one or more inorganic oxide materials; mixing the firstintermediate composition and the second intermediate composition to forman admixture; contacting the admixture with an effective quantity of apeptization agent to peptize the admixture and form a peptizedcomposite, wherein the peptization agent including one or more oxidizeddisulfide oil (ODSO) compounds; forming solid catalyst particles and/orsolid catalyst support particles from the peptized composite.
 11. Themethod as in claim 10, further comprising thermally treating thecatalyst particles.
 12. The method as in claim 10, wherein the firstintermediate composition comprises zeolite, amorphous alumina silicate,silica, metal salts, or a mixture comprising two or more of zeolite,amorphous silica alumina, silica or metal salts.
 13. The method as inclaim 10, wherein the first intermediate composition comprises a mixtureof zeolite and amorphous silica alumina.
 14. The method as in claim 9,wherein the peptization agent peptizes the surface of the solid catalystcomponents and increases adhesion.
 15. The method as in claim 10,wherein the inorganic oxide binder comprises alumina.
 16. The method asin claim 10, wherein contacting the admixture with the peptization agentcomprises mulling or kneading.
 17. The method as in claim 16, furthercomprising adding deionized water during mulling or kneading to increaseextrudability of the composite.
 18. The method as in claim 10, whereinthe ratio of a quantity of ODSO in the peptization agent to a quantityof the second intermediate composition is in the range of about 1:1 toabout 1:1000.
 19. The method as in claim 18, wherein the ratio of thequantity of ODSO in the peptization agent to the quantity of the secondintermediate composition is in the range of about 1:1 to about 1:20. 20.Solid catalyst particles and/or solid catalyst support particles formedaccording to the method as in claim 9, containing sulfur from the ODSOwithin the particles.
 21. (canceled)
 22. Solid catalyst particles and/orsolid catalyst support particles as in claim 20, which exhibit crushstrength in the range of about 20-30 Newtons (N) per millimeter.
 23. Themethod as in claim 10, wherein the one or more ODSO compounds isselected from the group consisting of compounds having the generalformula (R—SO—S—R′), (R—SOO—S—R′), (R—SOO—SO—R′), (R—SOO—SOO—R′),(R—SO—SO—R′), (R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SO—SO—OH),(R—SOO—SO—OH), (X—SO—OR) and (X—SOO—OR), where R and R′ are alkyl oraryl groups comprising 1-10 carbon atoms, and where X denotes esters andis (R—SO) or (R—SOO).
 24. The method as in claim 10, wherein the one ormore ODSO compounds is selected from the group consisting ofwater-soluble ODSO compounds having the general formula (R—SOO—SO—R′),(R—SOO—SOO—R′), (R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SOO—SO—OH), (X—SO—OR)and (X—SOO—OR), where R and R′ are alkyl or aryl groups comprising 1-10carbon atoms, and where X denotes esters and is (R—SO) or (R—SOO).